We have developed a novel strategy for the enantiospecific synthesis of substituted piperidine structures. Molecules containing the piperidine motif exhibit a wide array of interesting biological activities. Coniine and isofagomine are two representative examples of the piperidine family. (-)-Coniine is highly toxic and is a popular target for showcasing synthetic routes to piperidine ring systems. Isofagomine, on the other hand, has promising therapeutic applications as a glycosidase inhibitor and thus serves as a lead compound for the development of more powerful drugs. Our strategy for the synthesis of piperidines blends the enantioselectivity of an enzyme with the rich chemistry of organometallic catalysts. Using this coupled methodology we are able to access chiral, nonracemic piperidine motifs from achiral α,β-unsaturated aldehydes.